Azin dye and process of making same.



, v UNITED s'r-AT s PATENT OFFICE.

PHILIP? T1, OF LEVERKUSEN, NEAR COLOGNE, GERMANY, ASSIGNOR TO FAR'BEN- FABRIKEN VORM. FRIEDR. TIQN' or GERMANY.

BAYER & CO., OF ELBERFELD, GERMANY, A CORPORA- AZIN DYE AND PROCESS OF MAKING SAME.

N 0 Drawing;

To cill whom it may concern:

, Be it known that I, PHILIPP Orr, doctor of philosophy, chemist, citizen of the German Empire, residing at Leverkusen, near Cologne, Germany, Kingdom of Prussia, have invented new and useful Improvements in Azin Dyes and Processes of Making Same, of which the following is a specification.

I have found that azin dyestuffs can be prepared in a very simple manner and.with an almost quantitative yield by joint oxidation of paradiamins or their substitution products with and arylated 1.3-naphthylene diamins or their substitution products or derivatives thereof 6. g. the sulfonic acids, in the. presence of'small quantities of ammoniaeal cupric oxid by means of oxygen or air. The reaction is probably due to a. catalytic action o'tthe cupric oxid ammonia. The copper is used in such small quantities that it IS not necessary to remove it from thedyes. Any paradiamins, e. g. para-phenylene diamin or its sulfonic or carboxylic acids, 1.4-naphthylene diamin, or any substituted para-diamins having a free amino group may be used, c. g. aminoarylanilins, aminodiphenylamins, etc.

For the production of'my new azin dyes I prefer to oxidize aminodiphenylamin compounds or their derivatives with at least one free amino group 6. g. para-aminodiphenylman, para para dminnodiphenylamln, para amino diphenylamin sulfonic acids, inouoacetyl para para diaminodiphenylaiuin sulfonic acid, para-methoxy-para,- aminodiphenylamin sulfonic acid, orthomethoxy-para -aniinodiphenylamin sulfonic acid etc. together withmono-sul'fonic acids of a rylated 1.3-napl1tl1ylene diamins or their derivatives, 0. r diphenyl-1.3-naphthylcnediamiu-S- or Ssull'onic acids, ditolylsulfonic acids etc. i

The new dycstull's are dark powders soluble in water with from a color. soluble in concentrated sulfuric acid and dyeing wool from acid baths from violet to blue shades.

ln order to illustrate the new process more l'ully llul'ollou'ing examples are given, the parts llclug by weight:

.!'(I/// n/(,f t.) parts of diphcnyl-L3- naphthalent-diamilvH-sull'onig: acid and 29.4

parts' of para amino ort'lio -1nethoxyami- Specification of Letters fatent.

at least one free amino groupviolet to blue Patented Nov. 16,1909.

Application fi1ed October 15, 1908. ,Serial No. 457,849

nodiphenylamin sulfonic acid are dissolved in a mixture of about 300 parts of alcohol and 300 parts of Water with 9.0 parts of sodium carbonate. parts of a concentrated solution of an ammoniacalsolution of copper sulfate (containing about 2 parts of crystal-' lized copper sulfate) are added. The mixture is then heated to from 30-'50 C. and air is passed through it until the diphenylnaphthylenediamin sulfonic acidhas com pletely disappeared. The dyestuit separates frequently during cooling; if not it is pre- 'cipltated by the addition of common salt.

It is after being dried and pulverized a brown powder soluble in water with a blue color and soluble in concentrated sulfuric acid with a green color. It dyes wool from acid baths pure blue shades.

Example 9-39 parts of dipheny11.3- naphthylenediamin sulfonic acid and "26.4- parts of parr-aminodi'phenylaminoortho-sulton'ic acid are dissolved in a mixture of about 300 parts of alcohol and in 300 parts of Water with parts of sodium carbonate. After the addition of 5 parts of a concent ated annnoniacal solution of copper sulfate the mixture is heated to from 5() G. and a-current of air ispasscd through it until the diphenyluaphthylencdiamin sulfonic acid has-com fletely disappeared. The dycstutf separatesahnost completely during cooling. It is filtered ofi' and dried. It dyes wool violet shades.

lfrmmplc {'z.3$) parts of diphenyl 1.3- naphthylencdiamin T 8 sullonic acid and 20st parts of para. aminodiphenyla'minoortho sull'onic acid are dissolved in alcohol and water. 5 parts of a concentrated ammoniacal solution of coppersulfato are added and the solution is heated to from 30-5 C. A current of air is then passed through until the quantity of the dyestulf formed does not increase any more. T he dyestuif which separates on cooling is filteredotf and dried. It dyes Wool from acid baths reddish blue shades. "The dyestuffs can also be ob-* ammoniacal solution of copper sulfate are the 5 parts of a concentrated diainins'with at least one free amino group added. The mixture is then heated to from 3050 (J. and a slow current of air is passed through it until the diphenylnaphthylenedianiin has completely disappeared. Most of the dyestuif crystallizes dlll'll'tg cooling. It is completely separated by the addition of common salt, Its hydrochlorid dyes cotton inordanted with tannin violet shades.

To render it suitable for dyeing wool the dyestuti is converted in the usual way into a soluble sult'o compound by treatment with fuming sulfuric acid. The sulfonic acid thus prepared dyes wool violet shades.

Other para-diamins or other naphthylenediainins can be used.

Having now particularly described and ascertained the nature of my invention and in what manner the same is }o be performed, I declare that what I claim is:-

1. The process for producing dyestuffs ot' the azin series, which proces consists in oxidizing in the presence of ammoniacal cupric oxid by means of oxygen, as hcreinbefore defined, paradiamins and a'rylated 1.3-naphthylenediamins, substantially as described.

The process for producing dyestuffs of the azin series, which process consists in oxidizing in the presence of ammoniacal cu ric oxid by means of oxygen, as hereinbe ore defined, substitution products of paradiainins with at least one free amino group and arylated 1.3--naphthy1enediamins, substantially as described.

3.. The process forproducing dyestuffs of the azin series, which process consists in oxidizing in the presence of ammoniacal cupric oxid by means of oxygen, as hereinbefore defined para-diamins and sulfonic acids of arylated 1.3-naphtl1ylenediamius, substantially as described.

4. The process for producing dyestutl's ot the azin series, which process consists in oxidizing in the presence of ammoniacal cupric oxtid by means of oxygen, as hereinbet'ore defined, substitution products of paraand sulfonic acids of arylated 1.3-naphthylenediamins, substantially as described.

5. The process for producing new dyestuffs of the azin series, which process consists in oxidizing in the presence of ammoniacal cupric oxld by means of oxygen, as hereinbefore defined, amino-iiphenylamin compounds with at least one free amino group and monosulfonic acids of arylated 1.3- naphthylenediamins, substantially as. described.

6. The process for producing a new dyestuff of the azin series, which process con sists in oxidizing in the presence of ammoniacal cupric oxid by means of oxy en, as hereinbefore defir id, para-amino-ort o,- inethoxyaminodiphanylamin sulfonic acid and dipheny1-l.3-naphthylenedia1nin-8-sulfonic acid, substantially as described.

7. The process for producing dyestuffs ofthe azin series, which process consists in oxidizing in the presence of ammoniacal cupric axid by means of oxygen, as hereinbefore defined, para-diamins and arylated 1.3-naphthylenediamins and treating these compounds with sulfonating agents, substantially as described.

8. The herein-described new dyestuffs of the azin series obtainable from arylated 1.3- naphthylenediamin inonosulfonic acids and aininodiphenylamino compounds with atleast one free amino group, which dyestuffs are dark powders soluble in waterwith from a violet to blue color and soluble in concentrated sulfuric acid, and dyeing wool from acid baths from violet to blue shades, substantially as described.

9. The herein-described new dyestuff of the azin series, obtainable from diphenyl-L3- naphthylenediamin 8 sulfonic' acid and para -a1ninoortho methoxyaminodiphenlyamin sulfonic acid, which dyestufl? is after being dried and pulverized a brown owder soluhlc'in' water with a blue color, so uble in concentrated sulfuric acid with a green color and dyeing wool from acid baths pure blue shades, substantially as described.

In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses.

' jlzI-IILTPP OTT. [it s.] \Vitnesscs:

OTTO KGNIQ, Wu. WAsui'NcToN BRUNswIoK. 

